CN114230744A - Starch-based elastomer and preparation method and application thereof - Google Patents
Starch-based elastomer and preparation method and application thereof Download PDFInfo
- Publication number
- CN114230744A CN114230744A CN202210058916.7A CN202210058916A CN114230744A CN 114230744 A CN114230744 A CN 114230744A CN 202210058916 A CN202210058916 A CN 202210058916A CN 114230744 A CN114230744 A CN 114230744A
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- China
- Prior art keywords
- starch
- parts
- based elastomer
- modified starch
- preparation
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- Granted
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 105
- 239000008107 starch Substances 0.000 title claims abstract description 105
- 235000019698 starch Nutrition 0.000 title claims abstract description 105
- 239000000806 elastomer Substances 0.000 title claims abstract description 83
- 229920001971 elastomer Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229920000881 Modified starch Polymers 0.000 claims abstract description 56
- 239000004368 Modified starch Substances 0.000 claims abstract description 56
- 235000019426 modified starch Nutrition 0.000 claims abstract description 55
- -1 polypropylene carbonate Polymers 0.000 claims abstract description 42
- 239000010902 straw Substances 0.000 claims abstract description 34
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 30
- 150000003077 polyols Chemical class 0.000 claims abstract description 30
- 229920000379 polypropylene carbonate Polymers 0.000 claims abstract description 30
- 239000000945 filler Substances 0.000 claims abstract description 29
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 29
- 150000002009 diols Chemical class 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- 239000003963 antioxidant agent Substances 0.000 claims description 30
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000004970 Chain extender Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000004014 plasticizer Substances 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000000155 melt Substances 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000006065 biodegradation reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a starch-based elastomer and a preparation method and application thereof, wherein the preparation method comprises the following preparation raw materials: the modified starch is prepared from polypropylene carbonate polyol, polycaprolactone diol, modified starch, straw, a filler and an auxiliary agent; wherein the modified starch is iron ion modified starch. According to the invention, ferric ions and starch are utilized to form a complex, and a coordination cluster formed by coordination reaction has a physical crosslinking effect, so that the movement of a starch molecular chain can be limited, the shear viscosity of a melt is improved, the anti-plasticization effect is achieved, the extrusion residence time of the melt is increased, the shear degradation effect of a screw is further improved to a certain extent, and the strength and the thermal stability of the starch are improved. The elastomer prepared by using the modified starch has good mechanical property and degradability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a starch-based elastomer and a preparation method and application thereof.
Background
In order to reduce the white pollution caused by high molecular products, the development of new-generation plastic and elastomer products which have excellent properties and are degradable is dedicated at home and abroad. One of the materials is aliphatic polyester material, but the mechanical properties of the materials are poor and the processing window is narrow due to the problems of high crystallinity, secondary crystallization and the like caused by the high stereoregularity of the materials; on the other hand, the price of aliphatic polyester is several times that of common high molecular materials, and the industrial production is difficult to realize before the large-scale price reduction. And the thermoplastic material using natural polysaccharide macromolecules such as starch and the like as base materials, such as starch-based plastic plasticized by glycerol, glycol, sorbitol and the like, is degradable, but the mechanical property of the material is poor, and the application range is limited.
Therefore, there is a need to develop a starch-based elastomer that is degradable and has good mechanical properties.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: a starch-based elastomer, which is degradable and has good mechanical properties.
The second technical problem to be solved by the invention is as follows: a preparation method of the starch-based elastomer.
The third technical problem to be solved by the invention is as follows: the application of the starch-based elastomer is provided.
In order to solve the first technical problem, the technical scheme provided by the invention is as follows: a starch-based elastomer comprising the following raw materials: the modified starch is prepared from polypropylene carbonate polyol, polycaprolactone diol, modified starch, straw, a filler and an auxiliary agent;
wherein the modified starch is iron ion modified starch.
According to some embodiments of the invention, the adjunct comprises a chain extender, a catalyst, an antioxidant and a plasticizer.
During the processing, the chain extender is added, and the poly (propylene carbonate) polyol and the polycaprolactone diol can spread molecular chains and increase the molecular weight.
The addition of the antioxidant ensures that the composite material has stable performance and is not easy to age in the daily transportation and use processes.
The plasticizer is inserted between starch molecular chains to increase the distance between the molecular chains, thereby weakening the van der Waals force between the molecular chains, enabling the molecular chains to move easily, reducing the glass transition temperature of the starch polymer, increasing the plasticity, and enabling the starch to be processed easily, thereby enabling the starch to have thermoplastic processability.
According to some embodiments of the invention, the composition comprises the following raw materials in parts by weight: 40-50 parts of polypropylene carbonate polyol; 10-25 parts of polycaprolactone diol; 10-25 parts of modified starch; 20-40 parts of straw; 1-5 parts of a filler; 0.5-1 part of catalyst; 3-5 parts of an antioxidant; 5 to 10 parts of chain extender and 1 to 3 parts of plasticizer.
According to some embodiments of the present invention, the molecular weight of the polypropylene carbonate polyol is 2000 to 5000; preferably, the molecular weight of the polycaprolactone diol is 1000-4000.
The molecular weight is too large, which affects the tensile strength and hardness of the elastomer and reduces the tensile strength and hardness; too low a molecular weight can affect the elongation and set of the elastomer, and can degrade elongation and set properties.
According to some embodiments of the invention, the raw materials for preparing the iron ion-modified starch comprise starch and iron salt.
According to some embodiments of the invention, the iron salt comprises an organic iron salt.
According to some embodiments of the invention, the organic iron salt comprises a carboxylate.
According to some embodiments of the invention, the iron ion modified starch comprises the following preparation raw materials in parts by weight:
1 part of starch and 2-3 parts of iron salt.
According to some embodiments of the invention, the iron ion modified starch comprises the following preparation raw materials in parts by weight:
1 part of starch, 2-3 parts of ferric salt and 40-60 parts of water.
According to some embodiments of the invention, the method for preparing iron ion modified starch comprises the following steps:
preparing a starch solution, and adding the iron salt into the starch solution for reaction to obtain the iron-based catalyst.
According to some embodiments of the invention, the method of preparing a starch solution comprises the steps of:
and adding the starch into the water, and uniformly mixing at 80-100 ℃ to obtain the starch-containing water-soluble starch-based paint.
According to some embodiments of the invention, the temperature of the reaction is between 20 ℃ and 30 ℃.
According to some embodiments of the invention, the process is carried out for a period of 2h to 4 h.
According to some embodiments of the invention, the filler comprises a nano-filler.
According to some embodiments of the invention, the nanofiller comprises at least one of nano titanium dioxide and nano zinc oxide.
The addition of the nano titanium dioxide and the nano zinc oxide has the functions of self-cleaning and decontamination.
According to some embodiments of the invention, the nano-titania is modified nano-titania.
According to some embodiments of the invention, the modified nano-titania is carboxylated nano-titania.
According to some embodiments of the invention, the preparation of the carboxylated nano titania comprises the following steps:
s01, mixing n-butyl titanate, ethanol, citric acid and water, and adjusting the pH value to 2-4 to obtain sol;
s02, reacting the sol for 2-4 h at 60-80 ℃ under the protection of nitrogen, carrying out solid-liquid separation, collecting a solid phase, and washing to obtain the carboxylated nano titanium dioxide.
According to some embodiments of the invention, the molar ratio of n-butyl titanate, ethanol, citric acid and water is 1: 30-100: 5-10: 0.5 to 4.
According to some embodiments of the invention, the nano zinc oxide is a modified nano zinc oxide.
According to some embodiments of the invention, the modified nano zinc oxide is aminated zinc oxide.
According to some embodiments of the invention, the preparation of the aminated nano zinc oxide comprises the following steps:
s001, adding zinc acetate dihydrate into ethanol, refluxing for 1-2 h at 60-80 ℃, cooling to room temperature, adding KOH for reacting for 50-70 min, adding 3-aminopropyltriethoxysilane for reacting for 2-4 h, carrying out solid-liquid separation, collecting a solid phase, and washing to obtain the aminated nano zinc oxide.
According to some embodiments of the invention, the molar ratio of zinc acetate dihydrate, ethanol, KOH, and 3-aminopropyltriethoxysilane is 1: 30-100: 1.5-2.5: 1 to 10.
The nano material is modified and grafted to the main polymer body to disperse the nano material homogeneously in the elastomer.
According to some embodiments of the invention, the chain extender comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
According to some embodiments of the invention, the catalyst comprises at least one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, tin dioctoate, and dibutyltin dilaurate.
According to some embodiments of the invention, the antioxidant comprises one of a hindered phenolic antioxidant, a hindered amine antioxidant, a phosphite antioxidant, a sulfur-containing synergist, a benzofuranone derivative.
According to some embodiments of the invention, the plasticizer comprises at least one of formamide, glycerol, and urea.
The starch-based elastomer according to the embodiment of the invention has at least the following beneficial effects: according to the invention, ferric ions and starch are utilized to form a complex, and a coordination cluster formed by coordination reaction has a physical crosslinking effect, so that the movement of a starch molecular chain can be limited, the shear viscosity of a melt is improved, the anti-plasticization effect is achieved, the extrusion residence time of the melt is increased, the shear degradation effect of a screw is further improved to a certain extent, and the strength and the thermal stability of the starch are improved. The elastomer prepared by using the modified starch has good mechanical property and degradability.
To solve the second technical problem, the present invention provides the following technical solutions: the preparation method of the starch-based elastomer comprises the following steps:
s1, mixing modified starch and straws to form a premix;
s2, mixing the premix prepared in the step S1, the filler and the auxiliary agent, adding polycaprolactone glycol and polypropylene carbonate polyol, and mixing again to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, and extruding and granulating to obtain the starch-based elastomer.
According to some embodiments of the present invention, stirring is required during the mixing process in step S1; the stirring speed is 200 rpm/min-400 rpm/min; the stirring time is 5 min-10 min.
According to some embodiments of the present invention, the re-mixing in step S2 requires stirring; the rotating speed of the stirring is 900 rpm/min-1100 rpm/min; the stirring time is 20 min-30 min.
According to some embodiments of the invention, the operating parameters of the twin-screw granulator in step S3 are:
the temperature of a die head of the double-helix granulator is 120-180 ℃; the rotating speed of the screw is 300 rpm/min-500 rpm/min; the vacuum degree is 0.04 MPa-0.05 MPa.
The preparation method of the starch-based elastomer according to the embodiment of the invention has at least the following beneficial effects: the preparation method of the invention has simple process, and realizes the rapid preparation and large-scale production of the polyurethane elastomer.
In order to solve the third technical problem, the technical scheme provided by the invention is as follows: the starch-based elastomer is applied to the preparation of degradable materials.
According to the application of the embodiment of the invention, at least the following beneficial effects are achieved: the invention utilizes the synergistic effect of the polypropylene carbonate polyol, the polycaprolactone diol and the modified starch, so that the starch-based elastomer has good microbial degradability and maintains good mechanical property; the starch-based elastomer obtained by degradation performance tests has the mass loss of 86.5 percent and the elongation at break of more than 830 percent after being degraded for 90 days.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The preparation method of the carboxylated nano titanium dioxide selected in the embodiment of the invention comprises the following steps:
dissolving 1 weight part of n-butyl titanate in 30 weight parts of absolute ethyl alcohol, stirring for 20min by magnetic force, slowly dropwise adding a mixed solution of 10 weight parts of citric acid and 0.5 weight part of water, adjusting the pH value to 2 to obtain stable, uniform, clear and transparent pale yellow sol, heating and stirring for reaction at 80 ℃ under the protection of nitrogen, and then carrying out suction filtration, washing and drying to prepare the carboxylated titanium dioxide.
The preparation method of the aminated nano zinc oxide selected in the embodiment of the invention comprises the following steps:
adding 1 weight part of zinc acetate dihydrate into 30 weight parts of ethanol, refluxing for 2 hours at 80 ℃, cooling to room temperature, adding 2 weight parts of KOH for reacting for 60 minutes, adding 10 weight parts of 3-aminopropyltriethoxysilane for reacting for 3 hours, centrifuging, and washing to obtain the aminated nano zinc oxide.
The preparation method of the modified starch in the embodiment of the invention comprises the following steps:
firstly, uniformly mixing 2 parts by weight of starch and 100 parts by weight of water at 90 ℃, then adding 5 parts by weight of ferric acetate, and reacting for 2 hours at normal temperature (about 25 ℃) to obtain the modified starch.
Example 1 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 10 parts of polycaprolactone diol (Pasteur PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 part of catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 5 parts of a chain extender (isophorone diisocyanate, Bayer, CAS number: 4098-71-9) and 1 part of a plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.05 MPa.
Example 2 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 50 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-H2200); 25 parts of polycaprolactone diol (basf PCL 1000); 25 parts of modified starch; 40 parts of straw; 5 parts of a filler (carboxylated nano titanium dioxide); 1 part of catalyst (stannous octoate); 5 parts of antioxidant (Pasteur Tinuvin B75 ED); 10 parts of chain extender (BASF T-80) and 3 parts of plasticizer (urea).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10 min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.04-0.05 MPa.
Example 3 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 45 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 15 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; fillers (3 parts of carboxylated nano titanium dioxide and 2 parts of aminated nano zinc oxide); 0.81 part of catalyst (stannous octoate); antioxidants (Basff, antioxidant 1010, CAS number 6683-19-8); 8 parts of chain extender (Wanhua MDI-50) and 1 part of plasticizer (formamide).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10 min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.04-0.05 MPa.
Example 4 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 50 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-H2200); 20 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; 4 parts of a filler (zinc oxide); 1 part of catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 5 parts of a chain extender (BASF T-80) and 3 parts of a plasticizer (urea).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10 min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.04-0.05 MPa.
Example 5 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 45 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 25 parts of polycaprolactone diol (basf PCL 1000); 15 parts of modified starch; 30 parts of straw; 5 parts of a filler (aminated nano zinc oxide); catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 1 part of chain extender (BASF T-80)5 parts and plasticizer (urea) 3 parts.
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 5-10 min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 20-30 min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 120-180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.04-0.05 MPa.
Comparative example 1 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 10 parts of polycaprolactone diol (Pasteur PCL 1000); 10 parts of starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 part of catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 5 parts of a chain extender (isophorone diisocyanate, Bayer, CAS number: 4098-71-9) and 1 part of a plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting starch and straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min to uniformly mix the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.05 MPa.
Comparative example 2 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 10 parts of polycaprolactone diol (Pasteur PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 part of catalyst (stannous octoate); 3 parts of antioxidant (BASF, antioxidant 1010, CAS number: 6683-19-8) and 5 parts of chain extender (isophorone diisocyanate, Bayer, CAS number: 4098-71-9).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant and the chain extender into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.05 MPa.
Comparative example 3 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 40 parts of polypropylene carbonate polyol (Jiangsu Jinlong JLB-B2350); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 part of catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 5 parts of a chain extender (isophorone diisocyanate, Bayer, CAS number: 4098-71-9) and 1 part of a plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding the polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.05 MPa.
Comparative example 4 of the present invention is: the starch-based elastomer and the preparation method thereof are as follows:
the starch-based elastomer comprises the following preparation raw materials: 10 parts of polycaprolactone diol (Pasteur PCL 1000); 10 parts of modified starch; 20 parts of straw; 1 part of filler (nano titanium dioxide); 0.5 part of catalyst (stannous octoate); 3 parts of antioxidant (Basff, antioxidant 1010, CAS number: 6683-19-8); 5 parts of a chain extender (isophorone diisocyanate, Bayer, CAS number: 4098-71-9) and 1 part of a plasticizer (glycerol).
The preparation method of the starch-based elastomer comprises the following steps:
s1, putting the modified starch and the straws into a high-speed mixer, stirring at the rotating speed of 300rpm/min for 10min, and uniformly mixing the modified starch and the straws to form a premix;
s2, sequentially adding the premix prepared in the step S1, the filler, the catalyst, the antioxidant, the chain extender and the plasticizer into a high-speed mixer, then adding polycaprolactone diol and polypropylene carbonate polyol into the high-speed mixer, rotating at 1000rpm/min for 30min, and uniformly stirring the materials to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, melting and extruding and granulating to obtain the starch-based elastomer, wherein the die head temperature of the double-screw granulator is 180 ℃, the screw rotating speed is 400rpm/min, and the vacuum degree is 0.05 MPa.
And (3) performance testing:
(1) biodegradation test: the starch-based elastomers prepared in the examples and the comparative examples of the invention are subjected to extrusion casting to obtain starch-based elastomer films, the starch-based elastomer films prepared in the examples 1 to 5 and the comparative examples 1 to 4 are subjected to a soil burying decomposition test according to GB/T17603-2017, 10.0g of the films are buried underground, and the appearance and the weight loss of the films are tested after three months.
(2) And (3) testing physical and mechanical properties: the mechanical properties are in reference to GB/T1040-.
TABLE 1 test results of properties of starch-based elastomers prepared in examples one-five and comparative examples one-five
As can be seen from the data in Table 1, the starch-based elastomers prepared in examples 1 to 5 of the present invention have better degradation capability than the starch-based elastomers prepared in comparative examples one to five, and the wear resistance of the starch-based elastomers prepared in the present invention is significantly improved.
Compared with the embodiment 1, the common starch is used for replacing the modified starch in the comparative example 1 of the invention, the biodegradation degree of the prepared elastomer is 27.4 percent and is far lower than the biodegradation degree of 89.3 percent in the embodiment 1, and the mechanical property is poorer.
Compared with the example 1, the comparative example 2 of the invention does not add a plasticizer, and the processability of starch is poor, so that the mechanical property of the elastomer is reduced.
Compared with the embodiment 1, the comparative example 3 of the invention does not add polycaprolactone diol, the biodegradation degree of the prepared elastomer is 47.2 percent, which is far lower than the biodegradation degree of 89.3 percent in the embodiment 1, and the mechanical property is poorer.
Compared with the embodiment 1, the comparative example 4 of the invention has the advantages that the biodegradation degree of the prepared elastomer is 50.2 percent and is far lower than the biodegradation degree of 89.3 percent in the embodiment 1 without adding polypropylene carbonate polyol, and the mechanical property is poor.
According to comparative examples 1 to 4, the synergistic effect of the polypropylene carbonate polyol, the polycaprolactone diol and the modified starch is utilized, so that the starch-based elastomer has good microbial degradability and maintains good mechanical properties; the starch-based elastomer obtained by degradation performance tests has the mass loss of 86.5 percent and the elongation at break of more than 830 percent after being degraded for 90 days.
In conclusion, the invention utilizes the ferric ions and the starch to form the complex, the coordination cluster formed by the coordination reaction has the physical crosslinking function, the movement of the molecular chain of the starch can be limited, the shear viscosity of the melt is improved, the anti-plasticization function is realized, the extrusion residence time of the melt is increased, the shear degradation function of the screw is further improved to a certain extent, and the strength and the thermal stability of the starch are improved. The elastomer prepared by using the modified starch has good mechanical property and degradability.
While the embodiments of the present invention have been described in detail with reference to the description, the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A starch-based elastomer characterized by: the method comprises the following preparation raw materials: the modified starch is prepared from polypropylene carbonate polyol, polycaprolactone diol, modified starch, straw, a filler and an auxiliary agent;
wherein the modified starch is iron ion modified starch.
2. A starch-based elastomer according to claim 1, characterised in that: the auxiliary agent comprises a chain extender, a catalyst, an antioxidant and a plasticizer.
3. A starch-based elastomer according to claim 2, characterised in that: the composite material comprises the following raw materials in parts by weight: 40-50 parts of polypropylene carbonate polyol; 10-25 parts of polycaprolactone diol; 10-25 parts of modified starch; 20-40 parts of straw; 1-5 parts of a filler; 0.5-1 part of catalyst; 3-5 parts of an antioxidant; 5 to 10 parts of chain extender and 1 to 3 parts of plasticizer.
4. A starch-based elastomer according to any one of claims 1 to 3, characterized in that: the molecular weight of the polypropylene carbonate polyol is 2000-5000; preferably, the molecular weight of the polycaprolactone diol is 1000-4000.
5. A starch-based elastomer according to any one of claims 1 to 3, characterized in that: the raw materials for preparing the iron ion modified starch comprise starch and iron salt; preferably, the iron ion modified starch comprises the following preparation raw materials in parts by weight: 1 part of starch and 2-3 parts of ferric salt; preferably, the preparation method of the iron ion modified starch comprises the following steps: preparing a starch solution, and adding the iron salt into the starch solution for reaction to obtain the iron-based catalyst.
6. A starch-based elastomer according to any one of claims 1 to 3, characterized in that: the filler comprises a nanofiller; preferably, the nano filler comprises at least one of nano titanium dioxide and nano zinc oxide; more preferably, the nano titanium dioxide comprises modified nano titanium dioxide; more preferably, the nano zinc oxide comprises a modified nano zinc oxide.
7. A starch-based elastomer according to claim 2 or 3, characterised in that: the chain extender comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
8. A starch-based elastomer according to claim 2 or 3, characterised in that: the catalyst comprises at least one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, tin dioctoate and dibutyltin dilaurate; preferably, the antioxidant comprises one of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, sulfur-containing synergists and benzofuranone derivatives; preferably, the plasticizer includes at least one of formamide, glycerol, and urea.
9. A process for preparing the starch-based elastomer according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
s1, mixing modified starch and straws to form a premix;
s2, mixing the premix prepared in the step S1, the filler and the auxiliary agent, adding polycaprolactone glycol and polypropylene carbonate polyol, and mixing again to obtain a mixture;
and S3, adding the mixture prepared in the step S2 into a double-screw granulator, and extruding and granulating to obtain the starch-based elastomer.
10. Use of a starch-based elastomer according to any one of claims 1 to 8 for the preparation of a degradable material.
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